Certain bis-pyridinium compounds



United States Patent Int. Cl. C07d 31/32 US. Cl. 260-296 3 Claims This application is a division of application Ser. No. 455,333, filed May 12, 1965, and said latter application is a continuation-in-part of application Ser. No. 99,673, filed Mar. 31, 1961, and of application Ser. No. 404,525, filed Oct. 16, 1964, both now abandoned.

The present invention relates to a process for modifying polymeric compounds containing active hydrogen, and also relates to modifier reactants for use in such process. In addition, the invention relates to the modified polymeric materials produced in accordance with the aforementioned process.

The presence of certain substituents or side-chains in polymeric materials will alter the chemical and/ or physical properties of the polymer. Thus, polymers may desirably be modified or tailor-made to provide a preferred set of properties which will make the polymer suitable for a particular end use. It is theoretically possible to obtain a polymeric material with a desired set of properties, although such synthesis may be difficult or impossible for practical reasons. Thus, a more realistic approach to this problem involves starting with the basic polymer and treating it to introduce substituents or side-chains to impart the desired characteristics. In the case of naturally occurring polymers such as cellulose, starch, and keratin, the latter approach is the only possible course of action.

The polymeric materials with which the present invention is concerned are those which include active hydrogen. The active hydrogen may be in the form of hydroxy groups, amino groups and amide groups, for example. The polymeric materials of interest include the natural polymers such as starches, including the cereal starches, root starches and others, cellulose, regenerated cellulose and modified cellulose; proteins, polysaccharides; and other like materials. Among the synthetic polymeric materials with which the present invention is concerned are polyvinyl alcohol; partially saponified polyvinyl acetate; polyamines; polyamides; and the like. In short, any polymeric material in which the repeating group contains hydroxyl, amino, mercaptan and/or amide radicals is suitable for treatment in accordance with the present invention.

Among the prior art methods which have been used for the modification of polymers of the type discussed above is the reaction with activated olefinic compounds under basic conditions.

This reaction can be represented by the following generic equation:

In reaction (1), the symbol Pol-H is used to designate a repeating unit of the polymer which contains an active hydrogen (H), and W represents an activating radical, The use of an activating radical connected to the alpha carbon atom of an ethylenic radical to increase the reactivity of the alpha-beta double bond is well known. An activating radical is defined as an electron attracting radical which stabilizes carbon ions (Hine, Physical Organic Chemistry, 1956, p. 223) and induces polarization of the organic group to which it is linked. The activating 7 3,506,676 Patented Apr. 14, 1970 radical is also termed an electro-negative activating radical to indicate that the radical tends to withdraw electrons from conjugated systems, i.e., such groups are electron-attracting. This phenomenon is discussed in detail in Gould, Mechanism and Structure in Organic Chemistry, Holt, Rinehart, Winston-New York, 1959, Library of Congress Catalog Card No. 598696, pp. 217-218.

As indicated in the foregoing reference, the following are known electronegative activating radicals:

The following activated olefinic compounds are typical of those which may theoretically be utilized in recation Formula Name C H 0 11-0 N Acrylonitrile.

C I-I-C N Dinitrile of maleic acid. JHC N CH2= CH0 0 OH Acrylic acid.

ll CH2= CHCCH Methyl Vinyl ketone.

Acrolein. Acrylamide.

Formula Name C H CH= OHC O O H Crotonic acid. 0 H -OH= CHO O O R Alkyl crotonates.

II O= CH-OCH3 Mesityl oxide.

OH2= C0 0 0H l Methacrylic acid. CH

Each of the compounds shown in the above classes is characterized by the fact that the electronegative activating radical contains a terminal carbon atom which connects the activating radical to the ethylenic residue.

The use of activated compounds of the type set forth above for modifying textile fibers or fabrics made from active hydrogen-containing polymers has been of continuing interest. However, because of the practical limitations peculiar to the textile industry, it has not been possible to achieve the very desirable modifications which could be brought about by treatment of textile materials with modifying reactants of the type described above. Thus, for example, the activated olefinic compounds of the prior art are generally toxic and many of them exhibit lachrymatory and vesicant properties which severely limit their commercial usefulness. Extreme caution must be excised in handling these compounds, and it is usually necessary to provide a completely closed system in order to avoid the hazardous conditions which would otherwise prevail. The use of closed reaction vessels from which toxic vapors cannot escape is costly. It is feasible in the chemical manufacturing industry, but is is completely impractical in the textile industry where processing of fibers, yarns and fabrics is usually carried out in open equipment, and where a vast surface is exposed to the atmosphere during processing.

The activated olefinic compounds of the prior art are generally volatile. While losses through evaporation can be controlled by the use of reflux condensers and closed systems in the case of bulk reactions, this clearly cannot be accomplished in a practical manner when the reaction is carried out on textile materials in open equipment.

The solubility of the activated olefinic compounds in water is, in most instances, very low. Since water is an inexpensive and highly desirable reaction medium for the modification of polymers,- and particularly of textiles, compounds of limited water solubility are not suitable as reagents for the chemical modification of fibers.

The activated compounds often exhibit a strong tendency to polymerization and self-condensation. Thus, their reaction with the active hydrogen of the polymers is accompanied by the formation of homopolymers and graft polymers in an uncontrolled fashion. These by-products are often difficult to remove and may impair the properties of the modified polymers.

When the activated compounds are used in aqueous medium under alkaline conditions, they readily react with water, as indicated by the following equation:

H2O +WCH=CHz W-CH2OH2OH (2) Thus, by-products are formed, greatly decreasing the efficiency of the reagents and also decreasing the yield of modified polymer.

In view of the difficulties listed above, the activated olefinic compounds of the prior art have not generally been employed for the modification of polymers containing active hydrogen.

Accordingly, it is an object of the present invention to provide compounds which will perform in a manner similar to the prior art activated olefinic compounds, while at the same time being free from many of the undesirable characteristics of the prior art compounds.

It is another object of the present invention to provide a process for modifying polymers containing activated hydrogens in order to impart desirable characteristics to the polymers.

An additional object of the present invention is to provide polymers which have been modified by reaction with the compounds of the type contemplated by this invention.

In accordance with the present invention, a new class of activated compounds has been developed for use in modifying and treating polymeric materials containing active hydrogen. As a class, the active compounds of the present invention tend to be non-volatile, relatively nontoxic, and in many cases, water-soluble. Thus, treatment of polymers containing active hydrogen with the activated compounds of the present invention requires no special equipment and results in relatively high yields and the substantial absence of undesirable by-products.

One class of the activated compounds contemplated by the present invention may be represented by the following formula:

in which W represents an electronegative activating radical as defined above, R and R are selected from the group consisting of hydrogen and substituted and unsubstituted alkyl radicals of up to about five carbon atoms; and Y represents a polar residue derived from a reagent of weak nucleophilic character.

Typical activated compounds of the type shown by generic Formula 3 are as follows:

where W is CN, R and R are H, and Y is SSO Na.

o CNOHCHOl 3ClIa.

I; It 5) where W is CN, R and R are H, and Y is OCOCH In Formulas 4 and 5 above, W denotes the electronegative activating radical CN. Other typical electronegative activating radicals are also set forth above. It is to be appreciated that certain of the electronegative activating radicals may, in fact, be part of a larger organic structure which includes components which do not affect the activating influence exerted by the activating radical. Such organic structures are typified by the following:

where R may be hydrogen or an organic radical.

A system of nomenclature which may be used to define those compounds in which the electronegative activating radical is a part of a larger organic structure, as well as those compounds in which the electronegative activating radical alone is attached to the alpha carbon of the ethylenic residue, is as folows:

where X is CH C; R1 and R2 are H, and Y is -SSO;,Na.

It is to be appreciated that in some instances, X and W may be used interchangeably. Thus, for example, the compound of Formula 4 above, may be generally represented as follows:

where X is N, R and R are H, and Y is SSO Na.

As indicated, the radical Y is a polar residue derived from a reagent of weak nucleophilic character. Nucleophilic character is defined as the tendency to donate electrons or share them with a foreign atomic nucleus (GilmanOrganic Chemistrysecond edition-vol. II, p. 1859). Specifically, Y is the conjugate base of a Lowry- Bronsted acid which has a dissociation constant in water between about 5 10 and 5X10. (See Hine, Physical Organic Chemistry, second edition, McGraw-Hill, 1962, p, 43.)

Specific examples of Y are the following:

(a) Anion of a strong inorganic acid Sulfate.

-O S O 3 SSQ Thiosuliate. OPO Phosphate.

In which the negative charges are satisfied by suitable counter-ions such as alkali metal or ammonium.

(b) Anion of strong organic acid -0 C 0 CH Acetate. -O O OH Formate. -O C O C2115 Propionate.

(c) Cation of weak base N 05115 Pyridinium.

CH NCH Benzyl dimethylammonium.

CH2Ca s N C 11117 Isoquinollnium N (35H; Pieolinium.

Where the positive charge is satisfied by a suitable counter-ion such as halide.

The reaction of a polymeric material containing active hydrogen with an activated compound of the present invention may be represented by the following:

In the above Equation 10, the basic conditions under which the reaction is conducted catalyzes the splitting out of HY from the activated compound, thereby providing a double bond across which the act ve hydrogen-containing polymer may add. The alkaline environment also reduces the concentration of HY, thereby advantageously affecting the control of the reaction.

The specific reaction of cellulose with compound (4), shown above, may be represented by the following equation:

In reactions and (11), X, which includes the activating radical, and the polar residue Y, both exert an influence on the alpha and beta carbon atoms of the ethylenic residue of the activated compounds. The alpha carbon assumes a negative character and the beta carbon assumes a positive character. Under basic conditions, the radical HY is eliminated and is neutralized by the hydroxyl ions present. The unsaturated structure formed by splitting out HY then reacts with the polymeric material.

Thus, the activated compounds of the present invention serve the function of the prior are activated olefinic compounds, while at the same time eliminating the undesirable features of the prior art compounds. In the present invention, olefinic compounds are formed in situ, and reaction with the active hydrogen-containing polymers then occurs. By proper control of reaction conditions, the formation of olefinic compounds can be made to occur at a rate which is comparable to the rate at which such compounds react with the polymer. Accordingly, the concentration of the toxic, volatile, unsaturated compounds n the system at any given time may be maintained at a low value and the formation of undesirable by-products is effectively avoided.

The preparation of activated ethylenic compounds corresponding to Formula 6 above, can be carried out by several methods. The selected method of synthesis depends on the structure of the compound, and on the availability of suitable reactants. Some of the reactions R1 R2 R1 R2 (12) XCHCHA M2350 XCH(|1HSSO M MA R1 R2 R1 R2 (14) where X is an organic structure comprising an electronegative activating radical; R and R are selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl radical of up to five carbon atoms; M is selected from the group consisting of alkali metal ions and ammonium; A is halogen; and NaQ represents a teritary amine in which the three valences of the nitrogen atom are satisfied by means of carbon-nitrogen bonds, and in which Q is either (1) part of a heterocyclic ring of which the nitrogen atom is also a part, or (2) three monovalent radicals.

Set forth below are some examples which illustrates both the preparation of the activated ethylenic compounds of the present invention as well as their use in modifying or treating active hydrogen-containing polymers.

EXAMPLE 1 Preparation of cyanoethylthiosulfate (NCCH CH SSO Na) from acrylonitrile and sodium thiosulfate 248 g. (1 M) of sodium thiosulfate pentahydrate were dissolved in 248 ml. of buffer solution having a pH of 7.6 and prepared by dissolving 1.22 g. citric acid and 28.1 g. Na HPO in 1000 ml. of distilled Water. To this solution, 53 g. (1 M) of acrylonitrile were added dropwise. The temperature was maintained at 60 C. The liberated NaOH was neutralized by the gradual addition of glacial acetic acid. The pH was maintained between 6.5 and 8.0. After 9 hours reaction time, the conversion, calculated from the residual unreacted Na SSO was of the theoretical.

Analysis of the crude reaction mixture by alkaline hydrolysis gave a 16.4% bound thiosulfate content, corresponding to 19.6% cyanoethylthiosulfate in the solution. The yield calculated from the bound thiosulfate content was thus 64% of the theoretical.

EXAMPLE 2 Preparation of cyanoethylthiosudfate from B-chloropropionitrile and sodium thiosulfate 248 g. (1 M) Na S O -5H O dissolved in 248 ml. of water were mixed with 89.5 g. (I M) of ,B-chloropropionitrile dissolved in g. of ethanol. The reaction mixture was refluxed for 8 hours. The conversion, calculated from the residual unreacted Na S O was 97%.

After completion of the reaction, the alcohol and a portion of the water were removed under reduced pressure until a saturated solution was obtained. The pH of the solution was then adjusted to 7.0. This saturated solution (585 grams) contained 0.25% free Na S O and 28.3% cyanoethylthiosulfate, calculated from the bound Na S O content. The yield was 87.5% of the theoretical.

After keeping the saturated solution in a refrigerator overnight, white crystals were obtained. These were filtered, dried and analyzed for bound Na S O content. The equivalent weight, calculated from the results of this analysis was 222 (calculated 189). This corresponds to a dihydrate (calculated eq. wt. for dihydrate 225).

EXAMPLE 3 Preparation of cyanoethyl pyridinium chloride (NccHzol-rzl loslroor from acrylonitrile and pyridine hydrochloride 79.5 g. (1.5 M) of acrylonitrile and 448 g. of a 38.5% solution of pyridine hydrochloride in ethanol (corresponding to 172.5 g. (1.5 M) pyridine hydrochloride) were mixed with 400 g. ethanol, and ml. of triethylamine catalyst were added to the reaction mixture.

After standing for 3 days at room temperature, a portion of the solvent was removed under reduced pressure, and the concentrated solution was stored in a refrigerator overnight. White crystals separated out, and were filtered and dried.'The yield was 80% of the theoretical. The equivalent weight of the crystalline product, determined by electrometric titration with standard NaOH, was 181 (calcd. 168.5).

The ionic chloride content was 23.1% (calcd. 21.1%

EXAMPLE 4 Preparation of cyanoethyl pyridinium chloride from fi-chloropropionitrile and pyridine 89.5 g. (1 M) of ,B-chloropropionitrile and 79.1 g. (1 M) of pyridine were dissolved in 250 ml. of butyl alcohol. The reaction mixture was refluxed for 92 hours. The butanol was removed under reduced pressure. The residue (a solid waxy product) was heated at 65 C. for 3 hours at 5 mm. vacuum in order to remove residual solvent. The crude product so obtained had an equivalent weight (determined by electrometric titration with standard NaOH) of 185 (calcd. 168.5).

The ionic chloride content was 21.6% (calcd. 21.1%

The yield of product was 87% of the theoretical.

EXAMPLE 5 Preparation of cyanoethylacetate (NCCH CH OCOCH from ethylene cyanohydrin and acetic acid 71.1 g. (1 M) of ethylene cyanohydrin and 72 g. (1.2 M) of acetic acid were refluxed in 50 g. of benzene with l g. conc. sulfuric acid catalyst for 16 hours. The liberated 19 ml. water was distilled azeotropically through a Dean Stark moisture trap. The solvent was then removed under reduced pressure, and the residue was distilled in vacuo.

The product was obtained as a clear, colorless liquid boiling at 110-111 C. at mm. The yield was 86% of the theoretical.

EXAMPLE 6 (A) Preparation of cyanoethyl sulfate, ammonium salt (NCCH CH OSO NH 532.5 g. (7.5 M) of ethylene cyanohydrin were stirred and heated with 763.8 g. (7.5 M+5% excess) of sulfamic acid in the presence of 54.0 g. urea. The reaction was exothermic. By suitable control of the external heating, the temperature of the reaction mixture was maintained between 115 and 130 C. for one hour, and at the end of this time the reaction was complete. On cooling, the reaction mixture formed a solid white crystalline mass of crude product which had an equivalent weight of 173 (calcd. 168). The free sulfamic acid content of the crude product was lower than 1%. Even without purification, the ammonium salt of cyanoethyl sulfate was thus obtained in excellent purity. The yield was 92% of the theoretical.

If desired, the product could be further purified by crystallization from organic solvents, yielding a snow white crystalline powder, melting at 74-76 C.

(B) Preparation of cyanoethyl sulfate, sodium salt (NCCH CH OSO Na) 120 g. of a 38% aqueous solution of the ammonium salt of the cyanoethyl sulfate (product of Example 6(A)) was passed through an ion exchange resin column, which contained 200 ml. of wet Amberlite 1R-120H. The conversion to the free acid (as determined by titration of the solution obtained) was essentially quantitative.

60 g. of the solution of the free acid (containing 20.5% cyanoethyl sulfuric acid) were neutralized with sodium carbonate powder, and the water was removed under reduced pressure. The product which crystallized out was washed with acetone and obtained as a white crystalline solid melting at 176-178 C. Equivalent weight 184 (calcd. 173). The yield was 84% of the theoretical.

EXAMPLE 7 Preparation of carbamoethylthiosulfate (H NCOCH CH SSO Na) from fi-chloropropionamide 32.25 g. (0.3 M) of fi-chloropropionamide were dissolved in 32 g. of ethanol and the solution was mixed with 74.4 g. (0.3 M) Na S O -5H O dissolved in 74.4 ml. water. The reaction mixture was then refluxed for 10 hours. At the end of this time, of the thiosulfate present had reacted.

The alcohol and a portion of water were removed under reduced pressure, and a saturated solution was obtained. The solution (213 grams) contained 27% carbamoethylthiosulfate, as determined by analysis of the bound thiosulfate content. The yield was 86% of the theoretical.

EXAMPLE 8 Preparation of sodium salt of carboxyethylthiosulfate (NaOCOCH CH SSO Na) from uchloropropionic acid 124.0 g. (0.5 M) of Na S O -5H O were dissolved in 124 ml. of H 0. To this solution were added 54.25 g. (0.5 M) of B-chloropropionic acid dissolved in 166.2 g. of an aqueous solution containing 20 g. (0.5 M) of NaOH. The reaction mixture was refluxed for 8 hours, and the conversion achieved was 93.5% of the theoretical, calculated from the amount of Na S 0 consumed.

The alcohol and a portion of the water were then removed under reduced pressure until a saturated solution was obtained. This solution contained 41% of carboxyethylthiosulfate, calculated from the bound Na S O content and weighed 285 grams. The yield was therefore 97% of the theoretical.

EXAMPLE 9 Preparation of Bunte salt (HOCCH CH SSO Na) from acrolein and sodium thiosulfate 248 g. (1 M) of Na S O -5H O were dissolved in 248 g. of a buffer solution at pH=7.6 prepared as described in Example 1. 56 g. 1 M) of acrolein were added dropwise to this solution at room temperature. The pH of the reaction mixture was mintained between 6.5-8.0 by gradual addition of the glacial acetic acid in the course of reaction.

After 1 hour reaction time, the conversion calculated from the Na S O consumed was 73%, and a somewhat cloudy solution was obtained. After filtration, the solution was analyzed for bound Na s- 0 content and found to contain the desired product in 17% concentration. The acrolein odor was no longer noticeable, and the aqueous solution did not have any lachrymatory effect.

EXAMPLE 10 Preparation of bis-thiosulfate (NaO SSCH CH COOCH CH OCOCH CH SSO Na) from the bis-)B-chloropropionate of ethylene glycol 49.6 g. (0.2 M) of Na S O -5H O were dissolved in 50 ml. water, and the solution was mixed with 24.3 g. (0.1 M) of ethylene glycol bis-fl-chloropropionate dissolved in 25.0 g. of ethanol. The reaction mixture was refluxed for 8 hours.

The conversion, calculated from the Na S O consumption was 100%.

The clear aqueous solution so obtained contained 39.6% of the desired product, calculated from the value obtained analytically for the bound Na S O content.

EXAMPLE 11 Preparation of Bunte salt (CH COCH CH SSO Na) from methyl-vinyl-ketone 49.6 g. (0.2 M) of Na S O -H O were dissolved in 50.0 g. of a buffer solution at pH 7.6 prepared as described in Example 1. 14.0 g. (0.2 M) of methyl-vinyl-ketone were added dropwise to the thiosulfate solution at room temperature. The liberated NaOH was neutralized by adding glacial acetic acid to the reaction mixture. The pH was maintained between 6.5 and 8.0.

The conversion calculated from the Na S O consumption was 73%.

The solution contained 17.4% of the desired product, calculated from the value obtained analytically for the bound thiosulfate content.

EXAMPLE 12 Preparation of carboxyethyl pyridinium chloride (HOCOCH CH NC H Cl from acrylic acid and pyridine hydrochloride 36.0 g. (0.5 M) of acrylic acid and 180 g. of a 38.5% solution of pyridine hydrochloride in ethanol (corresponding to 0.6 M of pyridine hydrochloride), were dissolved in 300 g. of acetone, and 1 ml. of triethylamine catalyst was added to the reaction mixture. After 3 days reaction time at room temperature, a crop of white crystals was obtained. The equivalent weight of the crystalline product, determined by electrometric titration with standard NaOH solution was 188 (calcd. 187.5).

The ionic chloride content was 20.0% (calcd. 18.9%).

EXAMPLE 13 Preparation of carboxyethyl pyridinium chloride from ,B-chloropropionic acid and pyridine 43.4 g. (0.4 M) of fi-chloropropionic acid and 79.1 g. (1 M) of pyridine were refluxed in 200 ml. of petrol ether for hours.

The conversion was determined by analyzing the ionic chloride content of the reaction mixture, and found to be'50%. The crystalline product which precipitated was filtered and dried in a vacuum desiccator. The ionic chloride content of the crystalline porduct was 18.65% (calcd. 18.9%). The equivalent weight, determined by electrometric titration with standard NaOH solution, was 197 (calcd. 187.5).

EXAMPLE 14 Cyanoethylation of cotton fabric with cyanoethyl sulfate, ammonium salt (product of Example 6(A) above) (A) A sample of bleached, desized cotton fabric (80 x 80 print cloth) was treated on a laboratory padder with a 76% aqueous solution of the ammonium salt of cyanoethyl sulfate. The fabric retained 1.16 grams of solution per gram of fabric. After drying in a laboratory oven at 6070 C., the fabric was treated with a 35% solution of NaOH on a laboratory padder, and found to retain 0.59 gram of NaOH solution per gram of fabric. The ratio of NaOH to cyanoethylsulfate was thus about 0.5 equivalent. After standing wet for 60 minutes at room temperature, the sample was neutralized with a 5% acetic acid solution, washed in a 1% detergent solution at 50 C. for 15 minutes, and rinsed thoroughly.

The treated fabric exhibited greatly increased heat resistance. After 18 hours exposure to heat in an oven at C., the treated sample lost 44% of its tensile strength in the warp direction, while the untreated fabric lost 80 of its original tensile strength. The treated fabric also exhibited improved acid resistance. After treatment with a 20% solution of sulfuric acid at room temperature for 72 hours, the treated fabric lost only 26% of its Original tensile strength in the warp direction, while the untreated sample lost 54% of its tensile strength after the acid treatment.

(B) The procedure of Example 14(A) was repeated, but a 40% solution of NaOH was used in place of the 35 solution used above, and the sample was soaked in the NaOH solution for 1 minute before passing through the rolls of the laboratory padder. The ratio of NaOH to cyanoethylsulfate was 0.84 equivalent. After reacting at room temperature for 30 minutes, neutralizing and washing, the fabric showed a weight increase of 10.86%. This corresponds to a 45% yield of cyanoethyl groups introduced. The nitrogen content of the treated fabric determined analytically was 2.77% (calculated from the weight increase 2.86%).

After heat exposure for 18 hours at 80 C., the treated fabric lost only 32% of its warp tensile strength, and after treatment with 20% H 30 for 72 hours at room temperature, it lost only 24% of the original tensile strength in the warp direction.

(C) A cotton sample 80 x 80 print cloth) was padded with a 76% solution of cyanoethylsulfate at 116% wet pickup and after drying, it was soaked for 1 minute in a 35% solution of NaOH, and then passed through the 'rolls of a laboratory padder. The wet pickup of the NaOH solution was 82%. The ratio of NaOH to cyanoethylsulfate was 0.69 equivalent. After 60 minutes reaction time, the weight gain obtained was 9.18% corresponding to 38.0% yield.

Then the treated sample was exposed again to the same treatment. The total weight gain for the combined treatments was 19.71%. The nitrogen content was 4.43% (calculated from the weight gain 4.45%

(D) The double treatment procedure outlined in Example 14(C) was repeated, but in place of the 35% NaOH solution, a 40% NaOH solution was used, and the reaction time was decreased from 60 minutes to 30 minutes.

The total corrected weight gain was 19.6% (corresponding to a 42% yield). The nitrogen content was 4.63% (calculated from the weight gain 4.4%

After heat exposure, the sample lost only 23% and after acid treatment, only 17% of its original warp tensile strength.

EXAMPLE 15 Cyanoethylation of cotton fabric with cyanoethylsulfate, sodium salt (product of Example 6(B)) (A) A sample of bleached, desized cotton fabric was padded with a 44% aqueous solution of the product of Example 6(B). The wet pickup was The fabric was dried at 6070 C., then treated by padding with a 20% solution of sodium hydroxide. The ratio of NaOH to cyanoethylsulfate was 1.3. The Wet fabric was allowed to stand at room temperature for 30 minutes, then neutralized and washed. The weight increase was 8.7%, corresponding to a 54% yield of cyanoethyl groups introduced. The nitrogen content of the treated fabric was 2.37% (calculated from the weight increase 2.32%). The heat resistance and acid resistance of the treated fabric were outstanding.

(B) The procedure of Example 15 (A) was repeated, except that a 25% solution of NaOH was used, yielding a NaOH cyanoethylsulfate ratio of 1.8. The weight increases obtained were 11.6% (corresponding to a yield of 72%) and 13.5% (corresponding to a yield of 83%) for samples reacted 30 and 60 minutes, respectively.

1 1 EXAMPLE 16 Cyanoethylation of cotton with cyanoethylthiosulfate (product of Example 2) (A) A sample of bleached, desized cotton fabric (80 x 80 print cloth) was treated on a laboratory padder with a 26% solution of cyanoethylthiosulfate. After two consecutive paddings (with intermediate drying), a total of 0.47 gram of cyanoethylthiosulfate per gram of fabric was deposited on the fabric. After drying, the fabric was soaked for 1 minute in a 30% NaOH solution and passed through the rolls of a laboratory padder. The amount of NaOH deposited was 0.26 gram per gram of fabric. The ratio of NaOH to cyanoethylthiosulfate ratio was 2.4 equivalents. After 30 minutes reaction time at room temperature, the treated fabric was neutralized in a 5% acetic acid solution, then washed in 1% Triton X-100 solution at 160 F., for minutes.

The weight gain obtained was 6.1% after correcting for the difference in moisture regain between the treated and untreated fabric. This corresponds to a 45.5% reaction yield. The nitrogen content of the treated fabric was 1.63% (calculated from the weight gain 1.61%).

After 18 hours heat exposure at 80 C., the treated sample lost only 32% of its warp tensile strength, while an untreated control sample lost 82% of its warp tensile strength after the same heat exposure.

(B) The sample treated as outlined in Example 16(A), was exposed to the same treatment a second time. The total corrected weight gain was 11.7%. The nitrogen content was 2.15% (calculated from the weight gain 3.0%).

(C) The procedure of Example 16(A) was repeated, but instead of two paddings, three consecutive paddings were employed, resulting in depositing a total of 0.66 gram of cyanoethylthiosulfate per gram of fabric. The ratio of NaOH to cyanoethylthiosulfate was 1. 07 equivalents. The corrected weight gain obtained was 7.6% corresponding to a 41.0% yield of cyanoethylated cotton.

(D) The sample treated as outlined in Example 16(C) was treated again with two additional paddings. The total corrected weight gain was 11.5%, corresponding to an overall yield of 38.5%.

EXAMPLE l7 Cyanoethylation of rayon with cyanoethylthiosulfate, sodium salt A sample of rayon challis fabric was padded with a 28% cyanoethylthiosulfate solution at 95% wet pickup. After drying, the sample was padded with a 5% NaOH solution at 82.5% wet pickup. The NaOH/cyanoethylthiosulfate ratio was 0.73 equivalent. After 2 hours reaction time at room temperature, the treated sample was neutralized in 5% CH COOH solution, washed in a 1% detergent solution for 15 minutes, then rinsed thoroughly.

The weight gain was 2.6%, corresponding to a 34.6% yield.

Similar results were obtained when cyanoethyl sulfate was used in place of cyanoethylthiosulfate.

EXAMPLE l8 Cyanoethylation of starch with cyanoethylsulfate, ammonium salt 150 g. of corn starch were slurried with 180 ml. of water. Ninety-five grams of a 76% solution of the ammonium salt of cyanoethyl sulfate and 10 g. of 10% Triton X-100 solution or other nonionic wetting agent were then added to the reaction mixture. After 10 minutes stirring, 100 g. of a 34.3% NaOH solution were added to the reaction mixture. After reaction for one hour at room temperature, the cyanoethylated starch was filtered, washed with water several times and dried.

The nitrogen content was 2.08%, corresponding to a 50% reaction yield.

Ten grams of the modified starch were suspended in g. of water and the suspension was heated to the boil. A similar suspension prepared from unmodified starch was similarly heated. On standing at room temperature after cooling, the cyanoethylated starch suspension did not show any growth of mildew for 10 days. The suspension prepared from the untreated starch showed appreciable mildew growth after only 24 hours.

EXAMPLE l9 Cyanoethylation of cellophane A cellophane film was immersed in a 76% solution of the ammonium salt of cyanoethyl sulfate. Then it was wrapped in a cotton bag and centrifuged to wet pickup. The extracted cellophane sample was then soaked in a 35% NaOH solution for 1 minute, squeezed and allowed to stand for 30 minutes at room temperature. It was neutralized with 5% acetic acid solution and washed several times with cold water.

The nitrogen content of the cyanoethylated film was 2.18%, corresponding to a 31% reaction yield.

EXAMPLE 20 Cyanoethylation of polyvinyl alcohol Seventy-five grams of a polyvinyl alcohol resin (product marketed under the trade name of Elvanol 70-05 by the E. I. du Pont Co.) were dispersed in ml. of water. 47.5 g. of a 76% solution of the ammonium salt of cyanoethyl sulfate were added to the dispersion. After 10 minutes, 100 g. of 17.5% NaOH solution were added to the reaction mixture. After 1 hour reaction time at room temperature, the mixture was neutralized with 56% acetic acid solution.

The modified polyvinyl alcohol resin was precipitated with acetone from the neutralized reaction mixture, filtered, washed several times with acetone and dried in a desiccator.

Twenty grams of the product obtained were dispersed in 100 ml. of water at 70 C., and a film was cast from this dispersion. The film was dried at 65 C., for 2 hours, then washed several times in cold water in order to remove inorganic salts. The nitrogen content of the film so obtained was 1.01%.

EXAMPLE 21 Reaction of Bunte salt prepared from ethylene glycol bis chloropropionate and sodium thiosulfate (product of Example 10) with cotton A- sample of 80 x 80 print cloth was padded with a 39.6% solution of the product of Example 10 to a wet pickup of 82%. The padded sample was dried at 80 C., then it was treated with 20% NaOH solution to a wet pickup of 80%. The ratio of NaOH to reagent was 2.7 equivalents. After 30 minutes reaction time at room temperature, the treated sample was neutralized in dilute acetic acid solution, washed in detergent solution at 50 C., for 15 minutes, and rinsed. The weight gain obtained was 4.5%, corresponding to a reaction yield of 35.5%.

The treated sample was insoluble in cellulose solvents and had improved resistance to wrinkling, indicating that crosslinking had taken place by reaction of the bi-functional reagent with cellulose.

A particularly important activating group for use in conjunction with the present invention are ketones. Of particular advantage is the fact that the carbonyl carbon is divalent and therefore imparts a high degree of flexibility in the choice of the overall molecular structure of the activated compounds. One type of ketone-activated ethylenic compound contemplated by the present invention is shown by the following formula:

l R1 R2 (17) 13 where Q is a substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl or aralkyl radical and where R R and Y are as defined above. The notation X, as used and defined hereinabove, if used in Formula 17, would replace Q and the carbonyl radical:

Rx R2 If the notation W is used in a generic formula to cover the compound 17, the formula would be as follows:

However, it is expedient to use the Q notation in conjunction with the carbonyl radical to describe the ketoneactivated compounds of this invention.

The excellent results which can be obtained when polymers containing active hydrogen atoms are modified with the ketone-activated compounds of the present invention are particularly important for the following reasons. Unsaturated ketones containing the grouping are extremely reactive compounds. When R and R are hydrogen, the compounds tend to polymerize very rapidly, and it is virtually impossible to conduct addition reactions with active hydrogen-containing polymers using conventional techniques. For example, when methyl vinyl ketone (CH COCHCH is reacted with cellulose in the presence of an alkaline catalyst, it is necessary to employ up to a thousandfold excess reagent and the resulting modified cellulose must be extracted under vigorous conditions to remove deposits of the polymerized methyl vinyl ketone formed as a by-product. With divinyl ketone, the tendency to polymerization is even greater and the problem is multiplied. Furthermore, olefinic ketones have low vapor pressure, toxicity, and exhibit undesirable lachrymatory and vesicant properties.

When the ketone-activated compounds of the present invention are used, good yields of the desired reaction products are obtained even with moderate amounts of reagent, and even when the polymer is present in excess. No special techniques are required, and no significant amounts of polymeric by-products are formed. Thus, ketone modified polymers which could not be prepared heretofore by known techniques can be obtained. Of particular advantage is the fact that the ketone-activated compounds of this invention have low vapor pressures, reduced toxicities, and do not exhibit extreme lachrymatory or vesicant properties.

The preparation of ketone-modified polymers is a particularly desirable objective, since the carbonyl groups in the modified polymers constitute reactive sites which can be used for further modification of polymer properties.

In the treatment of polymers according to the present process, the polymer is contacted with a ketone-activated compound under basic conditions, and the reaction proceeds as follows:

R1 R2 1 R2 As described above, the excess base which is present catalyzes the splitting-out of HY and also reacts with the HY thus formed, thereby driving the reaction to comple tion by removing one of the products of the reaction.

Set forth below are several examples describing both the preparation of ketone-activated reactants and also the use of such reactants for the treatment of active hydrogen-containing polymers.

In the examples which follow, the results reported were obtained according to the following test methods:

U. Strtile, 1.Eucepa-Symposium,

EXAMPLE 22 Methyl (2-sodium thiosulfatoethyl) ketone (CH COCH CH SSO Na) 105.0 g. (1.5 mol) of methyl vinyl ketone were added dropwise at room temperature to 372.0 g. (1.5 mol) of Na S O -5H O dissolved in 360 ml. of water. Simultaneously with the addition of the ketone, glacial acetic acid was added at such a rate that the pH of the reaction mixture was maintained between 6 and 8. The addition required 2 hours and 81 g. (1.35 mol) of acetic acid were used to keep the pH in the desired range.

After the addition was completed, the neutral reaction mixture contained 0.22 mol of free thiosulfate and 1.28 mol of the desired product, as determined from the bound thiosulfate content of the reaction mixture.

The aqueous solution of the product was concentrated to 566 g. weight by partially removing the water under reduced pressure. A crystalline solid precipitated and was filtered. This solid, weighing 322 grams, contained some methyl thiosulfatoethyl ketone, sodium salt, and inorganic salts. The filtrate Weighing 234 grams, contained 1.0 mol (43.5%) of the desired product and was essentially free of inorganic salts.

EXAMPLE 23 4-acetoxybutanone-2; [methyl (2-acetoxyethyl) ketone- CH COOCH CH COCH] This compound was prepared by a method similar to that in US. Patent 2,857,442. Amberlite IRA-400 g.), an ion-exchange resin manufactured by Rohm and Haas, Philadelphia, Pa., was activated by soaking the resin overnight in 500 ml. of 10% aqueous sodium hydroxide. The resin was rinsed with distilled water until neutral, then soaked in 500 ml. glacial acetic acid. The acetic acid (960 g.) and methyl vinyl ketone (280 g.) were combined with the resin and the mixture was stirred for four days at room temperature. After removal of the resin, vacuum fractionation of the liquid gave 4-acetoxybutanone-2 as the fraction with B.P. 78-81 at 9 mm. (91 g.). Analysis of this sample by reaction with sodium hydroxide showed it to be 93%, pure.

EXAMPLE 24 Reaction of cellulose with methyl (2-sodium thiosulfatoethyl ketone (product of Example 22) A sample of plain weave cotton fabric (commonly known as 80 x 80 print cloth) was impregnated with a 25% aqueous solution of the product of Example 22, using a laboratory padder and setting the rolls at such a pressure as to give wet pickup; 0.3 gram of reagent were thus deposited per gram of cotton fabric. The fabric so treated was framed to the original dimensions and dried in a forced draft oven at 60 C., then treated by padding with an 8.5% aqueous KOH solution saturated with NaCl, setting the pad rolls at such a pressure as to give a 114% wet pickup. 0.097 g. of KOH were thus deposited per gram of fabric, corresponding to 1.16 equivalent of KOH per equivalent of ketone. The fabric was rolled smoothly on a rubber tube and allowed to stand at room temperature for five minutes, care being taken to prevent evaporation of water by covering the roll with polyethylene sheeting. The fabric was rinsed with a 1% acetic acid solution to neutralize residual KOH, then washed at 40-45" C. The

sample was framed and dried. The reaction yielded a 2.33% increase in fabric weight corresponding to 22.5% reaction yield. The carbonyl content of the fabric was found to be 0.35%.

EXAMPLE 25 Reaction of cellulose with methyl (Z-acetoxyethyl) ketone product of Example 23) 16 solution saturated with NaCl, the reaction time at room temperature was varied between 2 and 60 minutes. When 33 grams of reagent were deposited per 100 grams of fabric, and the amount of NaOH deposited was varied, the following results were obtained.

NaOH equiv. reagent Reaction Percent Percent equiv. time wt. gain yield 1. 2 6. 3 47 1. 25 10 7. 2 53 1. 60 10' 5. 6 41 1. 60 6. 8 49 1.43 60 8. 1 58 The treated fabric samples contained unsaturation and would be represented by a formula CeII-OCH CH COCH- CHCH In addition to the Examples set forth above, typical activated reactants of the type in which the activating group activates a single ethylene radical are as follows:

TABLE I Compounds 01 the type: X-Cl7H(I3HY Compound R1 R2 X Y 1 (HzNCOCHCHzIlICaHQCl' CH H -CONH2 (llIC H )C1- 2 OH COCHzOHzOSO NH4 H H CHzCO- -OSO3NH4 3 (CHgOOCHZOHQNCBHQCl H H omoo- (IlIC H5)C1- 4 HOCOCHCHzSSQ Na OH; H -CO0H SSO Na 5 NC-CHz-(FH-CN 11 --CN CN S S O3N8 6 CZH5(CFZCHZCHZI;IC5H5)CI H H C2H5CF2- (I;IC5H5)C1' 7 (CFaCHzCHzIlTCfiHQCl' H H CF (I;IC5H )C1- 8 (HOCH2COCH2CH2NC5H5)C1" H H HOCH2CO- (-NC5H5)C1- 9 CsH5CO(|3HCHzOSOaK CH3 H CeH CO- -OSO;K

1O CnHgsCOCHzCHzS S OaNB H H C11H35CO -S S OaNfl 11 ClCaH4COCH2CH2OCOCH3 H H ClCnHrCO -OCOCHa R f P too In Table I above, compounds 5 and 7 are such that NaOH weight *fi gj X represents the electronegative activating radical. s g p g 3 Found ilf 3 In the activated reactants described in detail thus far, Dem pe cc the splitting-out of HY from a reactant was occasioned 8'23 by the presence of one activating radical which operates 21 19 1 a single ethylenic residue. In other words, the splittingout of HY from a reactant was occasioned by the presence of an activating radical connected to the alpha car- EXAMPLE 26 bon of the ethylenic residue. With the ketone-activated Propenyl-2-sodium thiosulfatoethyl ketone (CH CH=CHCOCH CH SSO Na) EXAMPLE 27 Reaction of cellulose with propenyl-2-sodium-thiosulfatoethyl ketone Example 24 was repeated but the product of Example 26 was used from aqueous solution for the initial treatment. After the second padding with aqueous NaOH reactants, for example, it is possible to provide a structure in which a single carbonyl radical will serve to activate two ethylenic residues. In this manner, two reactive sites are provided in a single molecule. The reaction of active hydrogen-containing polymeric material with such a bifunctional compound results in cross-linking between polymeric molecules. Thus, the bifunctional compounds of this invention can be used for cross-linking cellulosic fabrics, for example, to impart resilience and dimensional stability. As will be shown by examples set forth hereafter, cross-linked polymers made in accordance with the present invention exhibit surprisingly good stability to hydrolysis in both acidic and alkaline media.

A formula for ketone activated reactants of the present invention in which one carbonyl radical activates two ethylenic residues is as follows:

R2 R1 R1 R2 (22) In addition to the ketone compounds, radicals such as Z-methoxyethyl-2'-acetoxyethyl ketone, the major contaminant being 2-acetoxyethy1 vinyl ketone.

EXAMPLE 30 may also be used to provide bifunctional structures. A R

eactron of cellulose with 2-methoxyethyl-2 generic formula for such compounds 15 as follows. acetoxyethyl ketone Y1( 3H( 3HW( 3H( JH-Yi Example 24 was repeated but the product of Example R1 (23) 29 was applied to cotton fabric from a dioxane-water solution in the initial padding. After padding with aqueous It is to be apprec1ated that Formula 22 may also be NaOH solution saturated with NaCl as described in EX- wntten as follows: ample 27, the reaction time was varied between 1 and 30 minutes. The following results were obtained, varying the concentration of reagent and NaOH (expressed as R1 R2 (24) grams per 100 grams of fabric).

NaOH

equiv. Reaction Percent Percent Percent reagent time wt. Percent Sample reagent NaOH equiv. min. gain yield with X being substituted for the organic structure: Analytical data for the treated samples (given below) indicate that the desired product corresponding to the o formula CellOCH CH OCH was obtained: Y-CH-CH-i'? Percent R2 R1 Percent 00 3 Sample Found Caled. Found Calcd.

Examples of the use of activated compounds which QZIIIIIII 312g 252 8:3? a? provide bifunctional structures of the type shown in Formula 23 are set forth below. EXAMPLE 31 EXAMPLE 28 2-methoxyethyl-2-sodium thiosulfatoethyl ketone Reaction of cellulose with Z-methoxyethylthiosulfato-ethyl-ketone Example 24 was repeated but the product of Example 28 was applied to cotton fabric from aqueous solution in the initial padding. After padding with aqueous NaOH solution saturated with NaCl, the samples were allowed to stand at room temperature for 10 and for 30 minutes. The following results were obtained when 33 grams of reagent per 100 grams of fabric and 8 grams of NaOH per 100 grams of fabric (equivalent ratio NaOH/reagent 1.5) were deposited in the treatment:

Percent 00 Percent 0 CH Percent Reaction wt. Percent Caled. Calcd. Sample time gain yield Found From W. G. Found From W. G.

radicals showed a 99% yield of 2 methoxyethyl-2'-sodium thiosulfato-ethyl ketone.

EXAMPLE 29 2-methoxyethyl-2-acetoxyethyl ketone (CH OCH CH COCH CH OCOCH Bis-(2-methoxyethyl) ketone (100 g.) was combined with glacial acetic acid (150 g.), acetic anhydride g.) and sodium acetate (10 g.). The solution was heated at l14-ll8 C. for 6 hours, while a distillate of methyl acetate (45 g.) was collected. The undistilled portion was poured into water, neutralized with sodium bicarbonate to pH 6.6 and extracted with chloroform.

Fractional distillation of the extract gave several fractions (total weight 27 g.), B.P. 72-84" at 0.4-0.7 mm., which were redistilled to give the desired product (12 g.), B.P. 90-92 C. at 1 mm. Examination of this product by gas-liquid chromatography indicated 85% purity as Curin Crease g temp, C.

Percent 00 recov., dry (W+F) Wet 1 Before curing:

19 EXAMPLE 32 Bis-(2-sodium thiosulfatoethyl) ketone (NaO SSCH CH COCH CH SSO Na) 20 The following results were obtained with varying percent concentrations of reagent and NaOH (expressed as grams deposited per 100 grams of cotton fabric).

Percent 5 Percent Percent Equiv. NaOH weight gain Sample reagent NaOH equiv./reagent Found 1 calculated A.. 36 12 1.30 8.7 9. B 26. 2 9. 2 1. 37 7. 3 6. 9 C 22. 7 8.4 1.45 6.2 6.0 D 16. 7 6. 7 1. 57 4. 7 4.4

1 Corrected for changes in moisture regain. The properties of the treated samples were as follows:

Percent Crease reeov. Percent shrinkage alter 10L Calcd. from Tear Str. Tens. Str. Found W. G. Dry Wet Warp Warp Warp Filling free and total thiosulfate radicals indicated a 76% yield of bis-(2-sodium thiosulfatoethyl) ketone.

EXAMPLE 33 Bis- (Z-pyridinium ketone dichloride [(CtHillICHtiCHaO O CHQOHZIiCHQZCl] Bis (2-chloroethyl)ketone (95 g.) was dissolved in ethanol (200 ml.) and treated with pyridine (107 g., 10% excess). The mixture was stirred for three hours at room temperature, then cooled to 5 C. and filtered to give the his pyridinium salt of bis-(2-chloroethyl) ketone (81 g.) as a hygroscopic, crystalline solid. On standing at 5 for two more days, an additional thirty-seven grams was obtained. Analysis of the product by titration with silver nitrate showed 22.4% chloride ion (calc. 22.7%, purity 98%). Analysis of the product by addition of a known excess of sodium hydroxide, followed by back-titration of the unconsumed alkali, gave an equivalent weight of 168 (calc. 156.5, purity 93% EXAMPLE 34 Bis- 2-acetoxyethyl) ketone CH COOCH CH COCH CH OCOCH Bis-(Z-methoxyethyl)ketone (200 g.) was combined with glacial acetic acid (300 g.), acetic anhydride (210 g.) and sodium acetate g.). The solution was heated at 120 C. for 11 hrs. while a distillate (168 g.) of methyl acetate was collected, B.P. 57-66 C. The undistilled portion was poured into water, neutralized with sodium bicarbonate to pH 6.3, and extracted with chloroform. Fractional distillation of the extract gave a fraction (43 g.) with B.P. 87-106 at 0.2 mm. with a refractive index at 27 of 1.4391. Analysis of this fraction showed 94% purity as bis-(2-acetoxyethyl)ketone.

EXAMPLE Reaction of cellulose with bis-(Z-pyridinium-ethyl)ketone dichloride (product of Example 33) Samples of 80 x 80 print cloth were impregnated with aqueous solutions of the product of Example 33 of various concentrations, using a laboratory padder. The fabric samples so treated were framed and dried in a forced draft oven at 60 C., then treated with aqueous NaOH solutions saturated with NaCl. After the second padding the samples were held flat for 1 minute, then rinsed in succession with 1% acetic acid solution, water, acetone, then washed thoroughly in dilute non ionic detergent solution at C. The samples were framed and dried.

The treated samples exhibited greatly improved crease recovery and dimensional stability, with only moderate losses in tensile and tear strength.

EXAMPLE 36 Reaction of cellulose with bis-(2-sodium thiosulfatoethyl)ketone (product of Example 32) Example 35 was repeated, using the aqueous solution of the product of Example 32 in place of the product of Example 33 for the initial fabric treatment. The following results were obtained in this experiment with varying concentrations of reagent and of NaOH (expressed as grams deposited per grams of fabric).

Percent Percent Percent Equiv. NaOH weight gain Sample reagent NaOH equiv./reagent Found 1 calculated l Corrected for changes in moisture regain.

The properties of the treated samples were as follows:

Reaction of cellulose with his (2-acetoxyethyl) ketone (product of Example 34) Example 35 was repeated but in place of an aqueous solution of the product of Example 33, a dioxane-water solution of the product of Exarnle 34 was used for the initial treatment. The following results were obtained with varying concentration of reagent and base.

Percent Percent Percent Equiv. NaOH weight gain Sample reagent NaOH cquivJreagent Found 1 calculated 1 Corrected for changes in moisture regain.

The treated samples had the following properties:

Percent Crease recovery (W+F) Tensile Calcd. strength Sample Found from W.G. Dry Wet warp EXAMPLE 38 Acid and alkaline hydrolysis of crosslinked cotton samples crosslinked with bifunctional ketones Percent 00 Crease Recov. (W+F) Hydrolysis Hydrolysis Sample 0 from Before After Before After Example 36 238 232 Example 36 1. 2 1. 1 267 262 It is apparent that the fabric properties were essentially unchanged after acid hydrolysis.

The alkaline hydrolysis was carried out at 65 C. for 60 minutes in a 0.5 N NaOH solution. (Liquor-fabric ratio 50:1.) The following results were obtained.

Percent 00 Wet Crease Reeov. Percent loss of Hydrolysis Hydrolysis Sample C wt after from hydrolysis Before After Before After Example 36- 0. 9 238 234 Example 35. 0. 4 1. 2 0. 74 267 266 It is apparent that even under conditions of drastic alkaline hydrolysis crosslinks formed as described for example in Examples 35 and 36 are exceedingly stable.

EXAMPLE 39 44.0 g. of a 10% aqueous solution of medium viscosity polyvinylalcohol (Elvanol 71-24, product of E. I. du Pont de Nemours & Co., Inc.) are mixed with 15.6 g. of the bis pyridinium salt of divinyl ketone (product of Example 33) at room temperature. A clear solution is obtained. When 24.0 grams of 25% aqueous NaOH solution are added, an insoluble gel precipitates out, which is filtered, neutralized with dilute acetic acid, washed thoroughly with water and dried in vacuum oven at 60-70" C. Weight of the product obtained: 8.3 g. CO content: 7.0%.

The modified polyvinyl alcohol is tested for water resistance. 1 g. sample is boiled in 25 ml. of water for 5 minutes, filtered, dried, and weighed. No weight loss was measured, proving the excellent water resistance of the product obtained.

EXAMPLE 40 25.0 grams of corn starch (Argo Corn Starch, manufactured by Best Foods) are stirred with 33 ml. of water at room temperature and then 1.8 grams of divinyl ketone bis pyridinium salt (product of Example 33) are added. When a homogeneous slurry is obtained, 22.5 g. of 3% aqueous NaOH solution are added. After stirring the mixture for 1 minute, it is allowed to stand at room temperature for 1 hour. The solid which settled out is filtered, neutralized with dilute acetic acid, washed thoroughly with water and dried in vacuum oven at 60-70 C. Weight of the product: 23.1 g. CO content: 0.5%.

A test portion of the solid product (1 gram) is suspended in 10 ml. of water and the Water is brought to boil. The modified starch product swells only very slightly and settles out on standing, while the unmodified starch forms a smooth viscous paste when tested by the same procedure.

EXAMPLE 41 When the procedure of Example 40 is repeated, using 8.3 grams of the ketone of Example 33 and 22.5 g. of 14% aqueous NaOH solution, 28.0 g. of the dried product are obtained. CO content: 1.3%. The properties of the modified corn starch are identical to those of the product of Example 40.

A very important class of compounds, not represented by Formula 23, in which the activating radical provides two reactive sites has the following generic formula:

Formula 25 can be written using the X notation as follows:

II where X is Q,C, R1 is GE -Y and R2 is H.

The examples below illustrate this aspect of the invention.

EXAMPLE 42 CHzO CO CH3 CHQCOCH OHzO O O CH:

118 g. (1.01 mol) of anhydrous a,a-dimethylol acetone and 255 g. (2.5 mol) of acetic anhydride were dissolved in 900 g. of ethyl acetate. Conc. H was added to this solution dropwise, until the reaction started to be exothermic. The temperature increased to 50 C. without external heating. After the exotherm subsided, the reaction mixture was heated to 80 C. for 2 hours. The reaction mixture was then cooled and poured into 2000 g. crushed ice. The organic phase was separated. The aqueous phase was extracted several times with ethylacetate and the extracts were combined with the organic phase. The combined organic phase was dried over anhydrous Na SO filtered and stripped under vacuo. After standing overnight in refrigerator, a crystalline solid (34 g.) was obtained from the residue on filtration. M.P.: 81-82 C.

Latent vinyl content: 24.5% (calcd. 26.7% By distilling the filtrate, 19 g. of distillate was obtained, which solidified in the recovering flask. B.P.: l50154 C. at 0.3-0.4 mm. Latent vinyl content: 24.9% (calcd. 26.7% Total yield of purified product: 26%.

23 EXAMPLE 43 Reaction of cellulose with bis('y,v-acetoxy-methyl) acetone (product of Example 42) Example 35 was repeated, but in place of an aqueous solution of the product of Example 33, a dioxane solution of the product of Example 42 was used for the initial treatment. The following results were obtained by varying reaction conditions.

defined by generic Formula 27. A typical compound is as follows:

Example above embodies two carboxylic activating radicals, each of which activates a separate leaving group. Other exmples describing compounds of this type are set forth below.

l Corrected for changes in moisture regain. The properties of the treated samples were as follows:

Percent loss of Crease Recov.

EXAMPLE 44 Dodeca-1,12-dipyridinium-3,9-dione-dichloride Percent carbonyl adgtfeggveilggt (W+F) s alllCHzoHzc O CH2)6C 0 CHzCH2N CrHa)2Cl-] Sample Found 933% gg f zgfi Dry Wet Dodeca-l,12-dichloro-3,9-dione (0.3 m.) was heated w1th pyridine (85 g., 1.07 m.) in ethanol at 80 C., for Q2 12 hours. The crude product was precipitated by the ad- 194 228 dition of 500 ml. acetone. The precipitated product was fig recrystallized from an ethanol-acetone-ether mixture. A

typical of those defined by Formula water-soluble solid was obtained.

Equivalent weight by saponification: 248; colculated 212.

Chloride content: 14.8%; calculated: 16.8%.

/CH2OCOCH3 T t d 1 14 d' ci 3 d d' 111 'd e ra ecaipyri iniumione- 1c on e crnoooon, m CH2HO5H5 U.) [(CgHgIlICH-zCHzC()(CHzhCOCHzCHzIfCrHQZCl 031110005 201- Tetradeca-i,14-dichloro-3,9-dione (100 g., 0.339 m.) was treated with pyridine (99 g., 1.24 m.) in ethanol at I 80 C., for 10 hours.

CHZSSOJNa 0 The major portion of the solvent and excess pyridine COCH was removed in vacuo. The crude product was precipitated by the addition of acetone and recrystallized from CHZSSOSNQ an ethanol-ether solvent mixture. A water-soluble solid was obtained.

Equivalent weight by saponification: 280; calculated: 227.5.

Chloride content: 12.6%; calculated: 15.6%.

EXAMPLE 46 Reaction of cellulose with dodeca-l,12-dipyridinium-3, 9-dione-dichloride (product of Example 44) Example 35 was repeated, but in place of an aqueous solution of the product of Example 33, an aqueous solution of the product of Example 44 was used for the nitial treatment. The following results were obtained by varymg reaction conditions:

Percent Percent Reaction Percent CO reagent NaOH Equiv. NaOH Time Percent Sample OWF OWF equiv. reeg. RT Yield Found Calcd A 27.9 6.2 1.0 36 hour 2.8 2. 9 B 27. 9 5. 2 1. 0 3 hours.- 2. 5 2.9 C 27. 9 8. 3 1. 57 hour. 100 2. 6 2. 0

Compounds of the type shown in Formula 26 may be represented by the following formula:

The properties of the treated samples were as follows:

Percent loss of added Crease reco E Q W2 E weight after 2m. (W-l-F) R R R R (27) 63 extraction in boiling 1 2 l 2 Sample MEK Dry W81; Using the X notation, the compound of Formula 26 may A be generically written as follows: a? Egg X?H |3HY 12 212 242 R R 28 where 2 EXAMPLE 47 In addition to the carbonyl activating radical, the amide structure can also be used in compounds of the type 7 Reaction of cellulose with tetradeca 1,14-dipyridinium-3, 9-dione dichloride (product of Example 45) Example 35 was repeated using an aqueous solution of the product of Example 45 in place of the product of EX- 25 ample 33 for the initial treatment. The following results were obtained by varying reaction conditions.

temperatures up to 100 C. Of course, increased temperatures provide accelerated reaction rates.

Properties of the treated samples were as follows:

In the activated reactants contemplated by the present invention, R and R are preferably hydrogen since this will avoid any steric hindrance problems and will generally provide the most reactive compounds. If the activating radical is particularly effective, such as a carbonyl group, then R and R can be more complex radicals without detracting from the advantages of the invention.

As can be seen from a study of the activated reactants, the activating radical is always attached to the alpha carbon of the ethylenic group through a carbon-to-carbon linkage. In other words, the activating radical must contain a terminal carbon atom by which it is connected to the ethylenic radical.

In treating active hydrogen-containing polymers with activated compounds of the type contemplated by the present invention, it is preferable to divide the treatment into two separate steps. Thus, for example, in the first step, the polymer may be treated with the activated com pound, and the treated polymer then contacted with an alkaline or basic medium. In this manner, the splittingout of the HY occurs at a time when the activated reactant is in contact with the polymer. Atlternatively, the po ymer may be treated first with a basic or alkaline mate rial and then subsequently exposed to the activated compound.

The choice of a solvent for treatment of active hydrogen-containing polymers in accordance with the present invention is not critical. Water is generally preferred because it is non-toxic and readily available. In addition, many of the more common alkaline-producing compounds are water-soluble.

Suitable alkaline compounds for use in processes of the present invention include alkali metal phosphates, carbonates, hydroxides, alkoxides and silicates; and quaternary ammonium hydroxides. Generally, compounds which are strong bases may be used, it being desirable that the alkaline reagent produce a pH above about 8 in a one-normal solution of water. Use of higher pH will provide an increase in the rate of reaction. Of course, care must be taken not to use a pH which will have an undesirable elfect on the particular polymer being treated.

The concentration of the activated compound may be varied within wide limits, depending on the structure of the polymer and of the compound; and also depending on the amonut of reaction desired. Good results are obtained with reactant-to-polymer proportions in the range of about to 50%, by weight. The amount of alkaline compound preferably should be at least equivalent to the amount of activated compound used.

The time and temperature of the reaction are variables which may be selected by one skilled in the art, and depend upon the concentrations used and the structures of the polymer and of the activated compound. The reaction period may vary from a few seconds to a few minutes at The active hydrogen-containing polymers which may be used in conjunction with the present invention have been described above from the standpoint of chemical structure. With respect to the physical characteristics or physical form of the polymers, there is a wide choice. Thus, the active hydrogen-containing polymers may be in the form of a solution, dispersion and the like. Alternatively, the polymer may be of the fiber-forming type and may be treated as a fiber, yarn, woven or other type of fabric, web, mat and the like. It is advantageous in many instances to utilize a swelling agent during the treatment of a polymer. Thus, for example, the treatment of cel ulose polymers of the present invention is desirably conducted in the presence of water.

The properties imparted to the polymers as the result of the processes described herein depend on the structure of the activated reactant and on the substituent group introduced. It is known, for example, that rot resistance, acid resistance and heat resistance can be imparted to cellulose by converting a small number of the available hydroxyl groups to the corresponding cyanoethyl ether grouping as indicated in the following equation:

The preparation of cyanoethyl ethers of cellulose by the methods of the present invention does not require the use of acrylonitrile which is a highly toxic and volatile compound; and can be carried out in open convention commercial equipment, using aqueous solutions. The yields of cyanoethylated polymer are good, no provisions are necessary for the recovery and purification of reagents, and the formation of by-products is minimized.

The introduction of cyanoethyl groups into soluble polymers such as starch and polyvinyl alcohol can be similarly achieved, the water sensitivity of the polymer can be decreased by the presence of the hydrophobic sub stituents (-OCH CH CN) and the resistance to mildew can be enhanced by the modification.

If, on the other hand, it is desired to increase the water solubility of an insoluble polymer, carboxyethyl groups can be introduced by the processes of the present invention. The preparation of polymers having valuable ion exchange properties by modification with suitable reagents is also possible. In fact, new functional groups can be introduced into polymers as desired, and many novel polymers having useful properties can thus be synthesized.

It is to be understood that the various examples and illustrative embodiments described above are intended to exemplify the present invention and variations can be made by one skilled in the art without departing from the spirit and scope of the invention.

What is claimed is:

1. A compound having the formula:

2. A compound having the formula:

3. A compound having the formula:

UNITED STATES PATENTS 3,031,435 8/1962 Tesoro et a1 260-79.3

5 HENRY R. JILES, Primary Examiner A. L. ROTMAN, Assistant Examiner US. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3.506.676 Dated April 1 1920 Inventor) Tesoro, G. and Sello, Stephen It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 1, Line #1: "hydroxy" should read --hydroxyl-- Col. 2, Line 19: :zrecatlon" should read --reaction-- Col. Line 3: is is should read ---it is--- Col. Line 52: the period after "H" should be a comma Col. fi, Line xgenerally" shouldri'ead "generically-- Col. Line 0 should be inse ed before --N-- Col. 5: Line 57: "are"should read --art-- Col. 6, Line 2% "NaQ." should read --N:Q-- Col. 6, Line 55: "sudfate" should read --sulfate-- Col. 8, Line 5 "mintained" should read --ma1ntained-- Col. 9, Line 27' a mz l nus-exponent line should appear after C1 C01. 9, Line 53: p rduct" should read --pr duct-- Col. 1 Line 25: a

"-C-C-CH" should read -C-C==CH I I I I 1 2 1 2 CO1. 13, Line 33: "CH COCHCH should read CH COCH=CH Col. 1 L, Line 38: "3" should appear after --COCH-- Col. l t, Line 55: a parenthesis should appear before "ketone" Col. 15, Line 7: a parenthesis should a pear before "product" Col. 15, Line 50: "0.8" should read --0. 2--

Col. 16, Line 13: the single bond line after "COCH" should be a double bond sign Col. 16, Table l: in the fifth column, "SSO Na" should be -SSO Na Col. lg, Line 72: "0" should appear after "84" Line 26: "Cel10CH CH OCH should read Cell0CH CH 5 g UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,506,676 Dated April 1M. 1970 Inventor) Tesoro, G. and Sello, Stephen P 2 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

j Col. 18, Line 64: delete first after" Col. 19, Line 30: "ethyl" should appear after pyridinium" Col. 20, Line 65: "examle" should read --exa.mple-- Col. 21, Line 30: "Wet" should appear before --crease-- Col. 23, Line 36: "HC should read --NC Col. 2 Line "ex ples" should read --exa.mples-- C01. 2 4, Line 29: "colculated" should read --calcu1ated-- Col. 24, Table: "reeg. in second column heading should read --reag.-- Col. 25, Line L3: "atlternatively" should read --alternatively-- Col. 25, Line 66: "emonut" should read --amount-- Signed and sealed this 30th day of March 1971.

(SEAL) Attest:

EDWARD M.FLETCHER,JR WILLIAM E. SCHUYLER, JR. Attesting Officer Commissioner of Patents 

1. A COMPOUND HAVING THE FORMULA: 1-(PYRID-1-YL-CH2-CH2-CO-CH2-CH2-)PYRIDINIUM 2CL(-) 